WO2020115142A1 - Method for recovering solvent and cellulose in the production of cellulosic spun-bonded nonwoven fabrics - Google Patents
Method for recovering solvent and cellulose in the production of cellulosic spun-bonded nonwoven fabrics Download PDFInfo
- Publication number
- WO2020115142A1 WO2020115142A1 PCT/EP2019/083693 EP2019083693W WO2020115142A1 WO 2020115142 A1 WO2020115142 A1 WO 2020115142A1 EP 2019083693 W EP2019083693 W EP 2019083693W WO 2020115142 A1 WO2020115142 A1 WO 2020115142A1
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- WO
- WIPO (PCT)
- Prior art keywords
- production
- spunbonded
- spunbond
- spinning
- solvent
- Prior art date
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Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
- D04H3/03—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments at random
- D04H3/033—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments at random reorientation immediately after yarn or filament formation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/02—Recovery or working-up of waste materials of solvents, plasticisers or unreacted monomers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D13/00—Complete machines for producing artificial threads
- D01D13/02—Elements of machines in combination
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/013—Regenerated cellulose series
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
Definitions
- the present invention relates to a plant for producing spunbonded fabric, comprising a spinning system, a device for dispensing coagulation liquid, at least one conveyor device for depositing the spunbonded fabric and a collecting device for the spunbonded fabric.
- the invention also relates to a method for recovering solvent or cellulose in a plant for producing spunbonded fabric, spunbond filaments extruded from a spinning system, laid down to form a spunbonded fabric and later collected.
- spunbonded nonwovens have been produced using the spunbond or meltblown process.
- filaments are extruded through a nozzle and drawn off and drawn by an underlying drawing unit.
- extruded filaments in the meltblown process as described, for example, in US Pat. No. 5,080,569, US Pat. No. 4,380,570 and US Pat. No. 5,695,377, are entrained and drawn by hot, fast process air as soon as they emerge from the nozzle.
- the filaments are deposited on a storage surface, for example a perforated conveyor belt in a tangled position to form a nonwoven fabric, transported to post-processing steps and finally wound up as nonwoven rolls.
- the known methods and devices have mainly been developed for the production of plastic filaments such as polypropylene, and the previous publications have mainly dealt with the nozzles, the raw material used and the storage systems necessary for the fleece storage.
- the economically sensible and safety-compliant operation of production systems requires a closer look at the operating states of spunbonded lines.
- the extruded filaments are either collected and disposed of by a device under the spinning system, or placed on a so-called carrier fleece. Since the carrier fleece was unrolled before the fleece deposit, on the one hand the conveyor belt is protected from damage by hot filaments and on the other hand the freshly extruded filaments are already transported and wound up via the subsequent consolidation and drying devices.
- the storage conveyor belt is prevented from being damaged by the hot filaments when it is spun on, and on the other hand, the spunbond is threaded automatically.
- the carrier fleece is cut off or torn off before the spunbond is deposited.
- the spunbonded fabric is then placed directly and directly on the storage surface. Before the system is switched off, the carrier fleece is unrolled again in order to be able to repeat the start-up procedure already described the next time it is started.
- spunbonded nonwovens for thermoplastic spunbonded special attention is paid to handling the hot melt and protecting the conveying device when starting up, switching off and when problems arise during the manufacture of spinbonded nonwovens.
- the transport of nonwovens for the production of cellulosic spunbonded fabrics has to solve additional tasks.
- the production of cellulosic spunbonded fabrics with the spundbond technology is described, for example, in US Pat. No. 8,366,988 and according to the meltblown technology in US Pat. No. 6,358,461 and US Pat. No. 6,306,334.
- the Lyocell spinning mass is drawn as in the already known spundbond and meltblown processes, but the filaments are additionally brought into contact with a coagulant before the fleece is deposited in order to regenerate the cellulose and to produce dimensionally stable filaments. Due to the turbulence of the air, the wet filaments are deposited as a nonwoven fabric in a tangled position.
- Solvents are used for the production of cellulosic spunbonded nonwovens, which have to be recovered.
- the spinning masses produced for example Lyocell spinning masses, are combustible and can cause damage to downstream system parts, so that the starting and stopping procedure cannot be carried out as with thermoplastic spunbonding lines.
- the initially coarse, hot, spun-filament filaments cannot simply be placed on a carrier fleece and transported over the dryer to the winder. It has been shown that when the system is started up, especially with low amounts of stretching air, the extruded filaments are still so coarse that even after the washing process described in WO 2018/071928 Al they have such high solvent residues that solvents are present in the further processing of the spunbonded nonwoven get lost.
- Downstream system parts such as the hydroentanglement, dryer and winder described in AT 503 625 are also contaminated and corroded by the solvent. In extreme cases, the solvent-loaded spunbonded fabric can still consist largely of spinning mass and start to burn in the dryer.
- the object of the present invention is therefore to avoid the disadvantages described above.
- the loss of solvent is to be minimized in the system mentioned at the beginning and in the method mentioned at the beginning, and the operational safety of downstream system parts is to be ensured.
- the object is achieved by a plant for the production of spunbond, comprising
- a collecting device for the spunbond is
- At least one ejection device is provided between the device for dispensing coagulation liquid and the collecting device for the spunbonded nonwoven.
- the object is achieved by a process for the recovery of solvent or cellulose in a plant for the production of spunbonded fabric, wherein spunbond filaments are extruded from a spinning system, drawn down into a spunbonded fabric and later collected, with the start-up of the plant, the shutdown of the plant or in the event of operational problems of the plant, spunbonded fabric is removed before being collected, with (a) the solvent being removed from the spunbonded fabric being removed and / or wherein (b) the spunbonded fabric which has been removed is fed to the production of the spinning solution.
- the system according to the invention fulfills the additional task of this solvent-laden spunbonded fabric, which does not have the desired properties, to be discharged and returned to the production process.
- NMMO which would have been lost when starting up and shutting down the system or in the event of production problems, could be specifically removed from the production system and subsequently recovered. It has been shown that the remaining cellulose after the solid / liquid separation, instead of being disposed of, can also be used again for spinning mass production.
- a further advantage of the method according to the invention in addition to the economically and environmentally improved operation of the spunbonded nonwoven system due to the solvent and cellulose recovery, is the protection of the downstream system parts. Since the solvent-loaded spunbonded fabric is discharged after the transport device or after the washing device or after the consolidation device, the combustible solvent or the spinning mass can be prevented from coming into contact with the hot dryer surface of a drying device.
- the spunbonded nonwoven is ejected with water jet prior to consolidation, it can also be prevented that solvent gets into the water cycle of the water jet consolidation, which can cause corrosion of the system parts and the nozzle strips at this point.
- Another advantage is the possibility of being able to discharge the spunbonded fabric at several points when starting up and shutting down the system, but also in the event of production disruptions, especially at high speeds. If, for example, the spunbonded fabric is wrapped around a vacuum drum or a deflecting roller during the water jet consolidation, the spunbonded fabric can be torn off and discharged, the speed of the water jet consolidation reduced, the entanglement eliminated and the system restarted without the entire spinning process or even the production of spinning mass to have to stop. Especially in the production of cellulosic Spunbonded webs have shown that spinning mass production should be carried out constantly in order to achieve uniform product quality.
- spunbonded nonwoven in normal operation is understood, on the one hand, to mean a non-woven structure made from regenerated cellulose filaments and, if appropriate, bonded at crossing points in the range from 0.1 pm to 250 pm filament diameter and with ⁇ 500 mg / kg solvent.
- spunbonded nonwoven is understood to mean a fabric made of partially or not regenerated spun mass filaments with a diameter of 0.1 to 50,000 ⁇ m and with a solvent concentration> 500 mg / kg up to a few million mg / kg when starting up, switching off or in the event of production disruptions.
- the actual state can also be between the two examples mentioned.
- the extruded filament mass filaments or already regenerated filaments can be discharged against the direction of transport after they have been deposited. If the spinning mass is not yet of the desired quality or if problems with downstream transport devices have to be eliminated, the discharge can take place immediately after the extrusion from the spinning system or in front of the transport device by moving the transport device backwards.
- the system can furthermore have at least one washing system, a discharge device being provided between the transport device and the washing system.
- the system can furthermore have at least one consolidation system, a discharge device being provided between the transport device and the consolidation system.
- the system can furthermore have a drying device, a discharge device being provided between the transport device or the previously connected solidification system and the drying device.
- the system can furthermore have a discharge device after the drying device.
- the transport device is in several parts and a discharge device is provided between two parts of the transport device.
- the transport device can e.g. be a conveyor belt. In the simplest case, it is a multi-part conveyor belt, the discharge device being arranged between two conveyor belt parts.
- the discharge device can have an opening for the spunbond to fall through.
- the discharge device is designed as a shaft under the gap between parts of the transport device.
- the gap between the conveyor devices can be between 2 and 200 cm, preferably 5 and 100 cm, more preferably 10 and 50 cm.
- the shaft can either cover the entire width of the transport device or only part of it.
- the spunbonded fabric can passively fall into the shaft and to the comminution device, or can be actively brought to the comminution device by air nozzles, water nozzles or other conveying devices known to the person skilled in the art.
- the discharged solvent-loaded spunbonded fabric can be recycled.
- a comminution device can be provided, the input of the comminution device being connected to the discharge device.
- the solvent-loaded spunbonded fabric can then be comminuted.
- the output of the comminution device is connected to the spinning solution production.
- the shredded material can be returned to the spunbond process.
- a further discharge device can be provided between the shredding device and the spinning solution production. In this case, too much shredded material can be retained or contaminated material can be completely excreted.
- a suspension container is provided between the shredding device and the spinning solution production. In this way, the shredded material can be ideally prepared for the next spinning process.
- the positions for discharging spunbonded fabric can vary according to the spinning system, the conveyor belt, after washing, after consolidation and after the dryer are, for example, to use edge trim material again for the production of spinning mass.
- Each discharge device can be followed by at least one comminution device and one suspension container. Depending on the system design, other design variants are possible.
- the discharged spunbonded fabric can also be transported from a plurality of discharge devices via conveying devices to a comminution device.
- the comminution device can have one suspension container or a plurality of suspension containers which are alternately filled. This means that the suspension tanks can be operated either continuously or discontinuously, depending on the system design. A suspension pump can continue the suspension.
- the suspension pump can be designed, for example, as a gear pump or worm gear pump.
- a screw conveyor, metering screw, a conveyor belt or a belt weigher can also be used
- the discharge process can take place at fleece transport speeds between 5 and 1000 m / min, preferably 10 and 500 m / min, even more preferably between 15 and 250 m / min.
- the conveyors can also be rotating rollers or drums.
- the discharge devices are adapted accordingly so that the spunbonded fabric is discharged at these points and the method according to the invention can be implemented.
- the discharged spunbonded fabric is suspended again before it is fed to the spinning solution production and mixed with fresh cellulose and fresh solvent.
- Spinning solution preparation is supplied, with the addition of solvent.
- Spinning mass production can be supplied and thus the NMMO and the already used Cellulose that has already been processed into spunbonded nonwoven can be dissolved and spun again without any restrictions in terms of spinnability or product properties.
- the process according to the invention can be used in the production of cellulosic spunbonded fabrics in order to recover the solvents used for dissolving the cellulose, for example tertiary amine oxides or ionic liquids.
- a method and a system are provided which allow the gaps or gaps between two system parts or transport devices to be used to discharge solvent-loaded spunbonded fabric, to crush the suspended spunbonded nonwovens, to suspend the suspension produced and either subsequently the solvent processing or add directly to the spinning mass production.
- the method according to the invention enables an economically, environmentally, safety and operationally improved operation of a spunbonded nonwoven system for the production of cellulosic spunbonded nonwovens, since the spunbonded nonwoven can be removed and settings can be made on downstream equipment without having to switch off the spinning mass production or the spinning system. Subsequently, the solvent can be recovered and contamination of downstream equipment can be prevented, thus minimizing the risk of corrosion and fire.
- Fig. 1 shows schematically a system according to the invention.
- Fig. 2 shows the viscosity of spinning pulp from fresh cellulose compared to reused cellulose from spunbonded nonwoven.
- Extruded and drawn spunbond filaments 5 are deposited by the spinning system 2 to form a spunbonded web 8 and are discharged at several discharge devices 14 by interrupting the main process flow.
- the filaments 5 can be sprayed with a coagulation liquid from a device 6 for dispensing coagulation liquid in order to add the cellulose Regenerate and stabilize the shape of the filaments 5 before the process air 4 and the filaments 5 impact on the transport device 7 in the form of a conveyor belt and the spunbonded fabric 8 is formed.
- the spunbonded nonwoven 4 is then washed in the main process flow in a washing device 10, optionally solidified in a consolidation system 11, dried in the drying device 12 and wound up into rolls in the collecting device 13.
- the gaps between conveyor belts 7, 9 are used to the extent that discharge devices 14 (not shown in more detail) can be installed which enable the solvent-loaded spunbonded fabric to be discharged.
- discharge devices 14 not shown in more detail
- a greater flexibility for the plant operators results from the removal from the main process flow, since they can carry out activities on downstream plant parts without the spinning solution production 3 and the spinning system 2 having to be shut down or throttled beforehand.
- the discharged spunbonded fabric is comminuted into spunbonded nonwoven pieces in a comminution device 15 and suspended in the suspension tank 16 by adding liquid 17 to such an extent that it is fed through, for example, a feed pump 18 either via line 19 to NMMO recovery (not shown in more detail) or via line 20 Spinning solution production 3 can be promoted (not shown). It has been shown that the discharged spunbonded fabric can be mixed into a transportable suspension by the comminution step and the mixing with liquid. This step makes the recovery of NMMO or the addition to the spinning solution possible.
- the discharge devices 14 can be located after the spinning material line, after the spinning system 2, before or after the transport device 7 and before or after the transport device 9 assigned to the washing device 10. In addition, discharge devices 14 can be between the solidification system 11 and the
- Drying device 12 are located.
- Discharge devices 14 can also be arranged after the drying device 12 and in front of the collecting device 13 in order to discharge products of poor quality, feed them to the recovery process and process them again into the spinning mass. Depending on the process control and plant layout, further positions for the discharge device 14 are also possible.
- a system 1 can therefore have one or more ejection devices 14.
- the moisture loading of the discharged spunbonded fabrics per kg of cellulose can be 0.1 kg / kg to 10 kg / kg in the area of the laundry and 0 to 4 kg / kg in the area after drying.
- the discharged spunbonded nonwoven is made via the discharge device 14
- the comminution device 15 can, for example, a mill, preferably a cutting mill, which can comminute 10 to 5000 kg / h, preferably 100 to 2000 kg / h, even more preferably 200 to 1000 kg / h of spunbonded nonwoven.
- the shredded spunbonded pieces are in the range from 10 pm to 100 mm in length, preferably 0.1 mm to 50 mm, even more preferably 1 mm to 10 mm in length.
- other comminution devices known to the person skilled in the art can also be used.
- the shredded spunbonded pieces are mixed with liquid 17 in the suspension container 16 and mixed to form a transportable suspension.
- the suspension container 16 can have an agitator in order to increase the homogeneity of the suspension.
- the suspension container can also be heated to the
- the liquid 17 used for the suspension can be demineralized water or a solution of the solvent and water used for the production of the dope.
- the liquid 17 for the suspension can have between 0 and 85% NMMO, preferably 10 to 80% NMMO, even more preferably between 20 and 78% NMMO.
- the suspension produced has between 1 to 95%, preferably 2 to 50%, even more preferably 3 to 30% cellulose content.
- the suspensions produced are either pumped for solvent recovery, or as an additive for spinning mass production, and the viscosity of the suspension varies greatly Depending on the cellulose content and the type of solvent, the cellulose content and the concentration of the solvent must be adjusted depending on the position of the ejection device (moisture content of the spunbonded fleece at this point) and the use of the suspension. It has been shown that the cellulose content of the suspension should preferably be below 20% if the suspension is transported for NMMO recovery, since later cleaning steps, the solid / liquid separation and subsequently the NMMO containment in the NMMO which is present anyway - Processing cycles of the Fyocell process can be carried out better. If the suspension is to be used again for the production of spinning mass, higher cellulose contents> 20% are advantageous since the cellulose content in the later spinning mass can be adjusted better.
- Fig. 2 shows that the viscosity of the spinning mass differs only slightly from the viscosity of a spinning mass made of fresh cellulose despite the renewed comminution and loosening of the spunbonded fabric (measurement using a rheometer Kinexus, from the Malvem measuring system CP4 / 40, oscillation measurement at 100 ° C. with 0.004 and 30Hz, evaluation with rSpace for Kinexus, both samples measured with the same cellulose and moisture content).
- spunbonded fabrics that have already been produced and are cast out can be reused.
- Fyocell spinning masses with 4 to 17% cellulose content can be produced from 100%, preferably 1 to 50%, even more preferably 2 to 30%, of reused cellulose from recovered spunbonded nonwoven.
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES19828571T ES2954478T3 (en) | 2018-12-05 | 2019-12-04 | Procedure for the recovery of solvents and cellulose in the production of cellulose nonwoven spunbond fabric |
JP2021531717A JP2022508316A (en) | 2018-12-05 | 2019-12-04 | Methods for Solvent and Cellulose Recirculation in the Production of Cellulose Spunbonded Nonwovens |
KR1020217020536A KR20210102915A (en) | 2018-12-05 | 2019-12-04 | Method of recycling solvent and cellulose in the manufacture of cellulose spunbonded nonwovens |
US17/299,828 US11939713B2 (en) | 2018-12-05 | 2019-12-04 | Method for recovering solvent and cellulose in the production of cellulosic spun-bonded nonwoven fabrics |
PL19828571.0T PL3891325T3 (en) | 2018-12-05 | 2019-12-04 | Method for solvent and cellulose recovery in the production of cellulose non-woven fabric |
FIEP19828571.0T FI3891325T3 (en) | 2018-12-05 | 2019-12-04 | Method for solvent and cellulose recovery in the production of cellulose non-woven fabric |
EP19828571.0A EP3891325B1 (en) | 2018-12-05 | 2019-12-04 | Method for solvent and cellulose recovery in the production of cellulose non-woven fabric |
CN201980080505.4A CN113195817B (en) | 2018-12-05 | 2019-12-04 | Method for recycling solvent and cellulose in the manufacture of cellulose spunbond nonwoven fabrics |
BR112021007831-2A BR112021007831A2 (en) | 2018-12-05 | 2019-12-04 | process for solvent and cellulose recovery in the production of non-woven fabric bonded by cellulosic spinning |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP18210510.6 | 2018-12-05 | ||
EP18210510 | 2018-12-05 |
Publications (1)
Publication Number | Publication Date |
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WO2020115142A1 true WO2020115142A1 (en) | 2020-06-11 |
Family
ID=64606896
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2019/083693 WO2020115142A1 (en) | 2018-12-05 | 2019-12-04 | Method for recovering solvent and cellulose in the production of cellulosic spun-bonded nonwoven fabrics |
Country Status (11)
Country | Link |
---|---|
US (1) | US11939713B2 (en) |
EP (1) | EP3891325B1 (en) |
JP (1) | JP2022508316A (en) |
KR (1) | KR20210102915A (en) |
CN (1) | CN113195817B (en) |
BR (1) | BR112021007831A2 (en) |
ES (1) | ES2954478T3 (en) |
FI (1) | FI3891325T3 (en) |
PL (1) | PL3891325T3 (en) |
TW (1) | TW202031950A (en) |
WO (1) | WO2020115142A1 (en) |
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2019
- 2019-11-22 TW TW108142508A patent/TW202031950A/en unknown
- 2019-12-04 CN CN201980080505.4A patent/CN113195817B/en active Active
- 2019-12-04 EP EP19828571.0A patent/EP3891325B1/en active Active
- 2019-12-04 ES ES19828571T patent/ES2954478T3/en active Active
- 2019-12-04 FI FIEP19828571.0T patent/FI3891325T3/en active
- 2019-12-04 KR KR1020217020536A patent/KR20210102915A/en unknown
- 2019-12-04 JP JP2021531717A patent/JP2022508316A/en active Pending
- 2019-12-04 PL PL19828571.0T patent/PL3891325T3/en unknown
- 2019-12-04 BR BR112021007831-2A patent/BR112021007831A2/en unknown
- 2019-12-04 WO PCT/EP2019/083693 patent/WO2020115142A1/en unknown
- 2019-12-04 US US17/299,828 patent/US11939713B2/en active Active
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BR112021007831A2 (en) | 2021-08-03 |
US11939713B2 (en) | 2024-03-26 |
TW202031950A (en) | 2020-09-01 |
CN113195817B (en) | 2023-05-23 |
FI3891325T3 (en) | 2023-09-08 |
PL3891325T3 (en) | 2023-10-09 |
CN113195817A (en) | 2021-07-30 |
ES2954478T3 (en) | 2023-11-22 |
JP2022508316A (en) | 2022-01-19 |
US20220106719A1 (en) | 2022-04-07 |
EP3891325B1 (en) | 2023-06-07 |
KR20210102915A (en) | 2021-08-20 |
EP3891325A1 (en) | 2021-10-13 |
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